scholarly journals Seasonal variation of peroxyacetylnitrate (PAN) in coastal Antarctica measured with a new instrument for the detection of sub-part per trillion mixing ratios of PAN

2007 ◽  
Vol 7 (17) ◽  
pp. 4589-4599 ◽  
Author(s):  
G. P. Mills ◽  
W. T. Sturges ◽  
R. A. Salmon ◽  
S. J.-B. Bauguitte ◽  
K. A. Read ◽  
...  
Keyword(s):  
Gas Phase ◽  
Research Station ◽  
Mixing Ratio ◽  
Gas Chromatograph ◽  
Mixing Ratios ◽  
New Instrument ◽  
Summer Minimum ◽  
Antarctic Boundary Layer ◽  
The Antarctic ◽  
Measurement Period

Abstract. An automated gas chromatograph with sample pre-concentration for the measurement of peroxyacetylnitrate (PAN) was constructed with a minimum detection limit below 1 pptv. This instrument was deployed at the British Antarctic Survey's Halley Research Station, Antarctica (75.6° S, 26.6° W) as part of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign. Hourly measurements were carried out between July 2004 and February 2005 with observed maximum and minimum mixing ratios of 52.3 and <0.6 pptv, respectively with a mean PAN mixing ratio for the measurement period of 9.2 pptv (standard deviation: 6.2 pptv). The changes in PAN mixing ratios typically occurred over periods of several days to a week and showed a strong similarity to the variation in alkenes. The mixing ratio of PAN at Halley has a possible seasonal cycle with a winter maximum and summer minimum, though the cycle is incomplete and the data are very variable. Calculations indicate that gross local PAN production is approximately 1 pptv d−1 in spring and 0.6 pptv d−1 in summer. Net loss of PAN transported to Halley in the summer is a small gas-phase source of NOx and net production of PAN in the spring is a very small NOx sink.

scholarly journals Seasonal variation of peroxyacetylnitrate (PAN) in coastal Antarctica measured with a new instrument for the detection of sub-part per trillion mixing ratios of PAN

2007 ◽  
Vol 7 (2) ◽  
pp. 5617-5645
Author(s):  
G. P. Mills ◽  
W. T. Sturges ◽  
R. A. Salmon ◽  
S. J.-B. Bauguitte ◽  
K. A. Read ◽  
...  
Keyword(s):  
Gas Phase ◽  
Research Station ◽  
Mixing Ratio ◽  
Gas Chromatograph ◽  
Mixing Ratios ◽  
New Instrument ◽  
Summer Minimum ◽  
Antarctic Boundary Layer ◽  
The Antarctic ◽  
Measurement Period

Abstract. An automated gas chromatograph with sample pre-concentration for the measurement of peroxyacetylnitrate (PAN) was constructed with a minimum detection limit below 1 pptv. This instrument was deployed at the British Antarctic Survey's Halley Research Station, Antarctica (75.6° S, 26.6° W) as part of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign. Hourly measurements were carried out between July 2004 and February 2005 with observed maximum and minimum mixing ratios of 52.3 and <0.6 pptv, respectively with a mean PAN mixing ratio for the measurement period of 9.2 pptv (standard deviation: 6.2 pptv). The changes in PAN mixing ratios typically occurred over periods of several days to a week and showed a strong similarity to the variation in alkenes. The mixing ratio of PAN at Halley has a possible seasonal cycle with a winter maximum and summer minimum, though the cycle is incomplete and the data is very variable. Calculations indicate that gross local PAN production is approximately 1pptv d−1 in spring and 0.6 pptv d−1 in summer. Net loss of PAN transported to Halley in the summer is a small gas-phase source of NOx and net production of PAN in the spring is a very small NOx sink .

scholarly journals Development and application of a new mobile LOPAP instrument for the measurement of HONO altitude profiles in the planetary boundary layer

2009 ◽  
Vol 2 (4) ◽  
pp. 2027-2054 ◽  
Author(s):  
R. Häseler ◽  
T. Brauers ◽  
F. Holland ◽  
A. Wahner
Keyword(s):  
Nitrous Acid ◽  
Ground Level ◽  
Concentration Profiles ◽  
Mixing Ratio ◽  
Above Ground Level ◽  
Mixing Ratios ◽  
New Instrument ◽  
Mobile Measurements ◽  
Southwest Germany ◽  
Absorption Technique

Abstract. The LOPAP (long path absorption) technique has been shown to be very sensitive for the detection of nitrous acid (HONO) in the atmosphere. However, current instruments were mainly built for ground based applications. Therefore, we designed a new LOPAP instrument to be more versatile for mobile measurements and to meet the requirements for airborne application. The detection limit of the new instrument is below 1 ppt at a time resolution of 5 to 7 min. As a first test, the instrument was successfully employed during the ZEPTER-1 campaign in July 2007 on board of the Zeppelin NT airship. During 15 flights on six days we measured HONO concentration profiles over southwest Germany, predominantly in the range between 100 m and 650 m above ground level. On average, a mixing ratio of 34 ppt was observed, almost independently of height. Within a econd campaign, ZEPTER-2 in fall 2008, higher HONO mixing ratios were observed in the Lake Constance area.

scholarly journals A single gas chromatograph for accurate atmospheric mixing ratio measurements of CO<sub>2</sub>, CH<sub>4</sub>, N<sub>2</sub>O, SF<sub>6</sub> and CO

2009 ◽  
Vol 2 (2) ◽  
pp. 549-559 ◽  
Author(s):  
S. van der Laan ◽  
R. E. M. Neubert ◽  
H. A. J. Meijer
Keyword(s):  
Research Station ◽  
Time Lags ◽  
Gas Chromatograph ◽  
Efficient System ◽  
Term Stability ◽  
Mixing Ratios ◽  
Long Term Stability ◽  
High Measurement ◽  
Cost Efficient

Abstract. We present an adapted gas chromatograph capable of measuring simultaneously and semi-continuously the atmospheric mixing ratios of the greenhouse gases CO2, CH4, N2O and SF6 and the trace gas CO with high precision and long-term stability. The novelty of our design is that all species are measured with only one device, making it a very cost-efficient system. No time lags are introduced between the measured mixing ratios. The system is designed to operate fully autonomously which makes it ideal for measurements at remote and unmanned stations. Only a small amount of sample air is needed, which makes this system also highly suitable for flask air measurements. In principle, only two reference cylinders are needed for daily operation and only one calibration per year against international WMO standards is sufficient to obtain high measurement precision and accuracy. The system described in this paper is in use since May 2006 at our atmospheric measurement site Lutjewad near Groningen, The Netherlands at 6°21´ E, 53°24´N, 1 m a.s.l. Results show the long-term stability of the system. Observed measurement precisions at our remote research station Lutjewad were: ±0.04 ppm for CO2, ±0.8 ppb for CH4, ±0.8 ppb for CO, ±0.3 ppb for N2O, and ±0.1 ppt for SF6. The ambient mixing ratios of all measured species as observed at station Lutjewad for the period of May 2007 to August 2008 are presented as well.

scholarly journals Portable calibrator for NO based on the photolysis of N<sub>2</sub>O and a combined NO<sub>2</sub>∕NO∕O<sub>3</sub> source for field calibrations of air pollution monitors

2020 ◽  
Vol 13 (2) ◽  
pp. 1001-1018 ◽  
Author(s):  
John W. Birks ◽  
Andrew A. Turnipseed ◽  
Peter C. Andersen ◽  
Craig J. Williford ◽  
Stanley Strunk ◽  
...  
Keyword(s):  
Air Pollution ◽  
Gas Phase ◽  
Phase Reaction ◽  
Calibration Source ◽  
Transfer Standard ◽  
Mixing Ratios ◽  
Wide Range ◽  
New Instrument ◽  
Gas Cylinders ◽  
Better Than

Abstract. A highly portable calibration source of nitric oxide (NO) based on the photolysis of nitrous oxide (N2O) supplied by 8 or 16 g disposable cartridges is demonstrated to serve as an accurate and reliable transfer standard for the calibration of NO monitors in the field. The instrument provides output mixing ratios in the range 0–1000 ppb with a precision and accuracy better than the greater of 3 ppb or 3 % of the target NO mixing ratio over a wide range of environmental conditions of ambient temperature (8.5–35.0 ∘C), pressure (745–1015 mbar corresponding to 2.7–0.0 km of elevation), and relative humidity (0 %–100 % RH). The combination of the NO calibration source with a previously described ozone calibration source based on the photolysis of oxygen in air provides a new instrument capable of outputting calibrated mixing ratios of NO, ozone (O3), and nitrogen dioxide (NO2), where the NO2 is produced by the stoichiometric gas-phase reaction of NO with O3. The portable NO2/NO/O3 calibration source requires no external gas cylinders and can be used for calibrations of NO, NO2, and O3 instruments for mixing ratios up to 1000, 500, and 1000 ppb, respectively. This portable calibrator may serve as a convenient transfer standard for field calibrations of ozone and NOx air pollution monitors.

scholarly journals Measuring atmospheric naphthalene with laser-induced fluorescence

2004 ◽  
Vol 4 (2) ◽  
pp. 563-569 ◽  
Author(s):  
M. Martinez ◽  
H. Harder ◽  
X. Ren ◽  
R. L. Lesher ◽  
W. H. Brune
Keyword(s):  
New York ◽  
New York City ◽  
Gas Phase ◽  
Laser Induced Fluorescence ◽  
Integration Time ◽  
Mixing Ratio ◽  
Quenching Rate ◽  
Anthropogenic Pollutants ◽  
Mixing Ratios ◽  
Instrument Configuration

Abstract. A new method for measuring gas-phase naphthalene in the atmosphere is based on laser-induced fluorescence at low pressure. The fluorescence spectrum of naphthalene near 308 nm was identified. Naphthalene fluorescence quenching by N, O and HO was investigated in the laboratory. No significant quenching was found for HO with mixing ratio up to 2.5%. The quenching rate of naphthalene fluorescence is (1.980.18) 10cmmolecules for N, and (2.480.08)10cmmolecules for O at 297 K. Instrument calibrations were performed with a range of naphthalene mixing ratios between 5 and 80 parts per billion by volume (ppbv, 10. In the current instrument configuration, the detection limit is estimated to be about 20 parts per trillion by volume (pptv, 10 with 2 confidence and a 1-min integration time. Measurements of atmospheric naphthalene in three cities, Nashville, TN, Houston, TX, and New York City, NY, are presented. Good correlation between naphthalene and major anthropogenic pollutants is found.

scholarly journals Portable Calibrator for NO Based on Photolysis of N<sub>2</sub>O and a Combined NO<sub>2</sub>/NO/O<sub>3</sub> Source for Field Calibrations of Air Pollution Monitors

2019 ◽  
Author(s):  
John W. Birks ◽  
Andrew A. Turnipseed ◽  
Peter C. Andersen ◽  
Craig J. Williford ◽  
Stanley Strunk ◽  
...  
Keyword(s):  
Air Pollution ◽  
Gas Phase ◽  
Phase Reaction ◽  
Calibration Source ◽  
Transfer Standard ◽  
Mixing Ratios ◽  
Wide Range ◽  
New Instrument ◽  
Gas Cylinders ◽  
Better Than

Abstract. A highly portable calibration source of nitric oxide (NO) based on photolysis of nitrous oxide (N2O) supplied by 8- or 16-g disposable cartridges is demonstrated to serve as an accurate and reliable transfer standard for the calibration of NO monitors in the field. The instrument provides output mixing ratios in the range 0–1,000 ppb with a precision and accuracy of better than the greater of 3 ppb or 3 % of the target NO mixing ratio over a wide range of environmental conditions of ambient temperature (8.5–35.0 °C), pressure (745–1,015 mbar corresponding to 2.7–0.0 km elevation) and relative humidity (0–100 % RH). Combination of the NO calibration source with a previously described ozone calibration source based on photolysis of oxygen in air provides a new instrument capable of outputting calibrated mixing ratios of NO, ozone (O3) and nitrogen dioxide (NO2), where the NO2 is produced by the stoichiometric gas-phase reaction of NO with O3. The portable NO2/NO/O3 calibration source requires no external gas cylinders and can be used for calibrations of NO, NO2 and O3 instruments for mixing ratios up to 1,000, 500, and 1,000 ppb, respectively. This portable calibrator may serve as a convenient transfer standard for field calibrations of ozone and NOx air pollution monitors.

scholarly journals Measuring atmospheric naphthalene with laser-induced fluorescence

2004 ◽  
Vol 4 (1) ◽  
pp. 343-363 ◽  
Author(s):  
M. Martinez ◽  
H. Harder ◽  
X. Ren ◽  
R. L. Lesher ◽  
W. H. Brune
Keyword(s):  
New York ◽  
New York City ◽  
Gas Phase ◽  
Laser Induced Fluorescence ◽  
Integration Time ◽  
Mixing Ratio ◽  
Quenching Rate ◽  
Anthropogenic Pollutants ◽  
Mixing Ratios ◽  
Instrument Configuration

Abstract. A new method for measuring gas-phase naphthalene in the atmosphere is based on laser-induced fluorescence at low pressure. The fluorescence spectrum of naphthalene near 308 nm was identified. Naphthalene fluorescence quenching by N2, O2 and H2O was investigated in the laboratory. No significant quenching was found for H2O with mixing ratio up to 2.5%. The quenching rate of naphthalene fluorescence is (1.98±0.18)×10−11 cm3 molecule−1 s−1 for N2, and (2.48±0.08)×10−10 cm3 molecule−1 s−1 for O2 at 297 K. Instrument calibrations were performed with a range of naphthalene mixing ratios between 5 and 80 parts per billion by volume (ppbv, 10−9. In the current instrument configuration, the detection limit is estimated to be about 20 parts per trillion by volume (pptv, 10−12) with 2σ confidence and a 1-min integration time. Measurement of atmospheric naphthalene in three cities, Nashville, TN, Houston, TX, and New York City, NY, are presented. Good correlation between naphthalene and major anthropogenic pollutants is found.

scholarly journals Coupling of HO<sub>x</sub>, NO<sub>x</sub> and halogen chemistry in the Antarctic boundary layer

2010 ◽  
Vol 10 (6) ◽  
pp. 15109-15165 ◽  
Author(s):  
W. J. Bloss ◽  
M. Camredon ◽  
J. D. Lee ◽  
D. E. Heard ◽  
J. M. C. Plane ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Layer Structure ◽  
Chemical Species ◽  
Austral Summer ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Physical Parameters ◽  
Research Station ◽  
Antarctic Boundary Layer ◽  
The Antarctic

Abstract. A modelling study of radical chemistry in the coastal Antarctic boundary layer, based upon observations performed in the course of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign at Halley Research Station in coastal Antarctica during the austral summer 2004/2005, is described: a detailed zero-dimensional photochemical box model was used, employing inorganic and organic reaction schemes drawn from the Master Chemical Mechanism, with additional halogen (iodine and bromine) reactions added. The model was constrained to observations of long-lived chemical species, measured photolysis rates and meteorological parameters, and the simulated levels of HOx, NOx and XO compared with those observed. The model was able to replicate the mean levels and diurnal variation in the halogen oxides IO and BrO, and to reproduce NOx levels and speciation very well. The NOx source term implemented compared well with that directly measured in the course of the CHABLIS experiments. The model systematically overestimated OH and HO2 levels, likely a consequence of the combined effects of (a) estimated physical parameters and (b) uncertainties within the halogen, particularly iodine, chemical scheme. The principal sources of HOx radicals were the photolysis and bromine-initiated oxidation of HCHO, together with O(1D)+H2O. The main sinks for HOx were peroxy radical self- and cross-reactions, with the sum of all halogen-mediated HOx loss processes accounting for 40% of the total sink. Reactions with the halogen monoxides dominated CH3O2–HO2–OH interconversion, with associated local chemical ozone destruction in place of the ozone production which is associated with radical cycling driven by the analogous NO reactions. The analysis highlights the need for observations of physical parameters such as aerosol surface area and boundary layer structure to constrain such calculations, and the dependence of simulated radical levels and ozone loss rates upon a number of uncertain kinetic and photochemical parameters for iodine species.

scholarly journals Stratospheric ozone chemistry in the Antarctic: what determines the lowest ozone values reached and their recovery?

2011 ◽  
Vol 11 (23) ◽  
pp. 12217-12226 ◽  
Author(s):  
J.-U. Grooß ◽  
K. Brautzsch ◽  
R. Pommrich ◽  
S. Solomon ◽  
R. Müller
Keyword(s):  
Gas Phase ◽  
Heterogeneous Reaction ◽  
Stratospheric Ozone ◽  
Ozone Production ◽  
Lagrangian Model ◽  
Model Parameters ◽  
Local Concentration ◽  
Mixing Ratios ◽  
Polar Stratospheric Cloud ◽  
The Antarctic

Abstract. Balloon-borne observations of ozone from the South Pole Station have been reported to reach ozone mixing ratios below the detection limit of about 10 ppbv at the 70 hPa level by late September. After reaching a minimum, ozone mixing ratios increase to above 1 ppmv on the 70 hPa level by late December. While the basic mechanisms causing the ozone hole have been known for more than 20 yr, the detailed chemical processes determining how low the local concentration can fall, and how it recovers from the minimum have not been explored so far. Both of these aspects are investigated here by analysing results from the Chemical Lagrangian Model of the Stratosphere (CLaMS). As ozone falls below about 0.5 ppmv, a balance is maintained by gas phase production of both HCl and HOCl followed by heterogeneous reaction between these two compounds in these simulations. Thereafter, a very rapid, irreversible chlorine deactivation into HCl can occur, either when ozone drops to values low enough for gas phase HCl production to exceed chlorine activation processes or when temperatures increase above the polar stratospheric cloud (PSC) threshold. As a consequence, the timing and mixing ratio of the minimum ozone depends sensitively on model parameters, including the ozone initialisation. The subsequent ozone increase between October and December is linked mainly to photochemical ozone production, caused by oxygen photolysis and by the oxidation of carbon monoxide and methane.

scholarly journals A single gas chromatograph for accurate atmospheric mixing ratio measurements of CO<sub>2</sub>, CH<sub>4</sub>, N<sub>2</sub>O, SF<sub>6</sub> and CO

2009 ◽  
Vol 2 (3) ◽  
pp. 1321-1349 ◽  
Author(s):  
S. van der Laan ◽  
R. E. M. Neubert ◽  
H. A. J. Meijer
Keyword(s):  
Research Station ◽  
Time Lags ◽  
Gas Chromatograph ◽  
Efficient System ◽  
Term Stability ◽  
Mixing Ratios ◽  
Long Term Stability ◽  
High Measurement ◽  
Cost Efficient

Abstract. We present an adapted gas chromatograph capable of measuring simultaneously and semi-continuously the atmospheric mixing ratios of the greenhouse gases CO2, CH4, N2O and SF6 and the trace gas CO with high precision and long-term stability. The novelty of our design is that all species are measured with only one device, making it a very cost-efficient system. No time lags are introduced between the measured mixing ratios. The system is designed to operate fully autonomously which makes it ideal for measurements at remote and unmanned stations. Only a small amount of sample air is needed, which makes this system also highly suitable for flask air measurements. In principle, only two reference cylinders are needed for daily operation and only one calibration per year against international WMO standards is sufficient to obtain high measurement precision and accuracy. The system described in this paper is in use since May 2006 at our atmospheric measurement site Lutjewad near Groningen, The Netherlands at 6°21' E, 53°24' N, 1 m a.s.l. Results show the long-term stability of the system. Observed measurement precisions at our remote research station Lutjewad were: ±0.04 ppm for CO2, ±0.8 ppb for CH4, ±0.8 ppb for CO, ±0.3 ppb for N2O, and ±0.1 ppt for SF6. The ambient mixing ratios of all measured species as observed at station Lutjewad for the period of May 2007 to August 2008 are presented as well.

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